Urea-aldehyde adhesive composition



as an adhesive'agent.

Patented Mar. 16, 1943 I UNITED srATEs PATENT" orrlcs Carleton Ellis,

Montclair, N. J.; Carleton Ellis,

In, Bertram Ellis, and Bank of Montclail',

executors of Carleton Ellis,

deceased, assignors to Ellis Laboratories, Inc.,a corporation of New J ersey.

No Drawing. Application March 16, 1940,

' Serial N0. 324,403

6 Claims. (01. 260-71) This invention relates to adhesive compositions which maybe applied to sheets or strips as thin filmsor coatings and thereby iumishadhesive or binding agents. This invention also involves 'adhesive or binding Compositions which are prepared from heat-hardening or thermosetting synthetic resins and which set or harden when subjected to a mild heating and pressure operation. This invention also includes adhesive compositions containing thermosetting synthetic resins and nitrohydroxy parafilns or derivatives thereof as hardening agents.

Synthetic resinous materials of the thermosetting type have been suggested previously as binding agents for the preparation of laminated objects such as those'made of paper or of wood. In such instances the individual strips of paper or wood, for example, are coated or impregnated with a syrup (usually aqueous) of the resinous material and afterwards subjected to pressure to secure a binding effect between the individual strips. If desired, simultaneously with the press-' ing operation, heat may be applied to obtain a firmer bond between layers making up the laminated object. Disadvantages of such operation are the coated or impregnated strips must be subjected to the pressing operation almost immediately aiterimpregnation with the syrup of resinous material, otherwise on evaporation or the solvent the resin bodies rapidly change to an infusible (and insoluble) state. When this occurs the resin is no longer applicablein the preparation of laminated objects.

It synthetic resins of the thermoplastic variety be employed, then since these resins never become permanently iniusible there is always the danger that a rise in temperature will cause the resinous bond to soiten. As a result the structure of the laminated object will be considerably weaker. It

is not inconceivable that the laminated object may disintegrate into its individual component parts should the increase in temperature be sufliciently high and considerable stress or strain simultaneously applied.

One object of this invention is the preparation of a binding agent coated or impregnated with a' I aldehyde.

' for example,

of an adhesive or binding strip which can be employed at slightly elevated temperatures to secure an adhesive bond which is not softened or destroyed after hardening by further application of heat.

Still another object of this invention is employment of specific hardening agents for the thermosetting Other objects will be apparent from the disclosures herein made.

I As previously mentioned, synthetic resins of the thermosetting variety are suitable for my purpose. Examples 0! such resins are those made from urea or derivatives thereof and an aldehyde and those These resinous bodies can be synthesized in any appropriate manner, the essential point being that when applied to strips of paper, the synthetic resins are still in the have not changed to an A syrupy soluuncured stage, i. e., they infusible and insoluble condition.

\ tion of these compounds is employed preferably I duced pressure) to thermosetting synthetic resinous body and capa- .ble of remaining in an active state for long periods of time. By the term remaining in'an active state is meant that the thermosetting resin is kept, for a considerable period of time, in a state or condition on the strip or sheet whereby it has not changed to the iniusible form but can be used Another object oi this invention a the mm other suitable solvent,

in water or other solvent which will evaporate quickly and spontaneously at room temperature and without the application of external heating. 11 desired, a

mixture of urea (or its derivatives) and a phenolic body may be reacted with an aldehyde to furnish resinous bodies applicable to this invention. Y

The syrupy solution 01 the synthetic resinous material may be secured by efiecting interaction 7 compounds in waterfior and'aiter interaction is a sumcient portion of the by distillation under reof the resin-forming complete then removing reaction medium (e. 'g.,

5. y evaporation under reduced pressure orby subjecting the liquid mass tion. The substantially dry, solid materials thereby obtained aiterward may be dissolved in'an appropriate solvent to yield a solution of the desired concentration and viscosity.

The syrupy or viscous solution or the resinous body, after incorporation of a hardening agent 1 at slightly elevated tempera-: tures, is applied to the strip of paper (or other which is effective suitable material) so as to impregnate and/or coat the latter with evaporation of the solvent, the strip then will possess a coating or film of the thermosetting resin and the hardening agent.

Compounds such as hexamethylenetetramine' resins suitable for my purpose.

made mm phenolic bodies and an give a liquid solution of the desired viscosity and concentration. In other instances it may be preferable to remove substantially all-oi the liquid'reaction medium,

to a spray-drying operathe said solution. After and alkali metal salts of halogenated acetic acid may be employed as the hardening agents, if

desired. However, the preferred agents for thisinvention comprise nitrohydroxy paraflins and.

derivatives .thereof, as for example, carboxylic esters, formals and acetals. The nitrohydroxy compounds are secured by interaction of an aliphatic aldehyde and a nitroparaflin and may contain one or more hydroxyl groups per molecule. Thus, one mole of nitroethane and one mole of formaldehyde may be reacted (in the presence of a basic catalyst such as calcium hydroxide) to furnish mainly the compound 2- nitropropanol. Should a nitroglyc'ol be desired, the molal proportion'of-aldehydemust be twice that of the nitroparaffln. For example, interaction of one mole of l-nitropropane and two .moles of acetaldehyde (in the presence of an alkali contact agent) gives principally the com-, pound 3-ethyl-3-nitropentanediol-2,4. From niexample of a suitable liquid. Methyl or ethyl alcohol can be substituted in many instances for acetone. Methyl ethyl ketone or methyl acetate are other illustrations of appropriate materials.

' Such materials being rapidly volatile at ordinary within the pores and fibers of the strip serving (preferably under reduced pressure), by extrac tion with an immiscible solvent, or by any other convenient means. .Other liquid media, e. g.,

alcohols or esters, maybe substituted for water in some cases. When the nitrohydroxy paraffin is a solid (e. g., a nitroglycol) then evaporation of the liquid reaction medium, followed by recrystallization of the residue from an appropriate solvent (for example, a mixture of ethyl acetate and chloroform) will yield a substantially pure product.

These nitroalcohols or nitroglycols in turn furnish derivatives, as mentioned above, which are suitable for my purpose. To illustrate, 2-nitro- 3-lnrdroxypentane (from l-nitropropane and acetaldeh'yde) can be treated with acetic anhydride (or other aliphatic acid anhydride) to yield the corresponding ester. Again, the nitroglycol, 2-methyl-2-nitropropanediol-l,3, can be reacted with formaldehyde in the presence of an acidic catalyst (e. g., hydrogen chloride) to furnish the corresponding formal. Acetaldehyde or other aliphatic aldehydes may besubstituted forformaldehyde. These nitrohydroxy paraflins and their derivatives, regardless of whether they are liquid or solid compounds, are suitable as hardeni-ng agents for the adhesive compositions made according to my invention.

As previously stated, aresinous syrup (preferably in water) is prepared. To this is added a solution or emulsion of the hardening agent in the same liquid. After these two liquid compositions are incorporated into one another by thoroughly mixing, the resulting preparation is employed in the impregnation of paper strips and the like. The latter operation may be conducted in any suitable manner, as for example, immersing the paper strips in the resin-containing solution and then afterwards passing them between rollers whereby excess liquid is removed.

The resin-impregnated and wet strip is sprayed with a liquid which is rapidly volatile at room temperature, is miscible with the liquid employed in preparing the resin syrup, and does not dissolve the resinous binding agent. Acetone is an 75 as the backing for the adhesive composition.

After the resin-impregnated and/or -coated strips have dried, a thin coating of wax is placed on them. This may be done by dipping the strips in a solution of wax in a volatile solvent. Spraying with such a solution is another procedure. Waxes suitable for my purpose include beeswax. ceresin, montan and paraflln waxes and the like. These need be only sufficiently soluble in the rapidly volatile organic solvents (acetone, alcohol, ketones, etc.) that after subjecting the resinimpregnated strip to a solution of wax, rapid spontaneous evaporation of the solvent will occur and the strip will be coated or covered with a thin wax film. The latter not only prevents-individual strips (should they be fabricated in the form of a pad or piled one upon another) from sticking to each other but also absorption of moisture from the atmosphere.

These three effects, namely, rapid drying'of the resin-impregnated strip, depositionof resin within the strip itself, and protection of the resin from moisture by means of a wax film, furnish ad-' hesive strips (according to this invention) in which the thermosetting resin will remain in a fusible and soluble state for prolonged periods of time. In fact some strips, prepared as indicated above, have been stored for 8 to 10 Weeks and at the end of this period were still active adhesive compositions.

It is possible, of course, to spray the wet resinimpregnated strip with a solution of wax in a volatile solvent. Thereby evaporation of liquids from-the strip and subsequent drying thereof will be hastened and simultaneously a thin film of wax will be obtained. However, in the preferred procedure each step, i. e., drying and film-forming, is

conducted in successive stages.

stances, after the paper strips are impregnated with the resinous composition they are allowed to dry by spontaneous evaporation of the solvent. No spraying,-or other treatment with volatile materials is needed to secure quick drying. The strips when dry may be-sprayed with or dipped into a solution of wax to secure a thin wax film over the resinous coating.

Such adhesive strips made according to this invention are useful for a variety of purposes, as for example, furnishing the adhesive bond between two sheets of paper, for mounting photographs or post cards in albums, for attaching labels to fabrics and the like. In applying such compositions for the purposes .just'mentioned, a convenient method of application isas follows: A strip containing the adhesive is placed between the two non-adhering surfaces and the three elements then are placed upon .a hard smooth surface. A hot object, e. g., a small hand iron, is moved rapidly back and forth for a few seconds. Simultaneously, some pressure should be exerted flow and form a bond with and impregnated surfaces and then to change to the non-soluble and non-fusible Y perature must burning, scorching or other undesirable effects.

. prepared by mixing 1 droxide as catalyst.)

so that the three'objectsarebrought into close contact with each other. Thisprocedure warms the adhesive strip thereby causing the resin to the non-impregnated very quickly state.

The temperature during this operation should be about 100 to -150- C. and will be determined by the type'and thickness of material employed with the adhesive strip. In any event, the temnotbe sufilciently high to cause Also, in most instances the time required to secure a good binding effect will be very short, often about 3 to 5 seconds. This value, of course, may vary somewhat with the thickness,'heat conductivity and other properties of the materials at hand. However, with many materials, such as post cardsphotographs, etc., the timeis very short and only a few seconds are required.

'The following examples will illustrate my invention and how it may be carried out.

Example 1.A syrupy liquid composition was 11.4 parts of dry phenolformaldehyde resin, 8 parts of acetone and 0.6 part of 2-nitro-2-methylpropanol. (The nitroalcohol was made by condensing equimolar proportions'of 2-nltropropane and formaldehyde in comprised thefollowing steps:

stance contained the following proportion of ingredients:

Parts Phenol-formaldehyde resin "-15.?

Acetone Formal of 2-nitropropanol Preparation of the formal of alkali. The resulting nitroalcohol, 2-nitropropanol afterwards was reacted with an equivalent proportion of paraform, using hydrogen chloride syrup, dried, and

the presence of a small quantity of calcium hy- 3o Strips of tissue pa er were immersed in this syrup, then withdrawn, and the, excess solution removed byscraping with the edge of a spatula.

When the strips were dry they were dipped in a saturated solution of paraffin wax in carbon tetrachloride and the latter was allowed to evapcrate spontaneously at room temperature.

These strips weretested in the following man-' her. A resin-impregnated strip was placed between two pieces of untreated paper, placed on a hard smooth surface, and then heat and pressure applied to the mass for a few seconds with the aid of a hot iron. After allowing the mass to cool for about 30 seconds. a bond was formed betweeneach of the outersheets and the interposed resinimpregnated strip. Also, the pieces of paper could not be pulled away from one another without tearing or splitting.

'Emmple 2.A syrupy liquid composition was prepared having the following proportion of ingredients: I

Parts Dry phenol-formaldehyde resin 8 Arca a 8 Acetal of 2-nitro-2-ethylpropanediol-1,3--- 0.4

The acetal was made in the following manner: 1- nitropropane and formaldehyde, in the ratio of 1. mole of the former to 2 moles of the latter, were reacted using calcium hydroxide as a catalyst. The resulting nitroglycol (i. e., 2-nitro-2-ethylprcpanediol-l,3) was treated with acetaldehyde, employing hydrogen chloride as a catalyst.

Parts Dried urea-formaldehyde resin 12.5 Water 12.5

as the catalyst.

Strips of paper were impregnated with this then coated with a thin film of parafiin wax, as described in Example 1. When these stripswere tested as adhesive compositions, as in Example 1, it was found they gave-very good binding action. Example 4.--A syrupy liquid prepared by dissolving 25 parts of, dry ureaformaldehyde resin in 25 parts of water and then incorporating'lz parts of 2-nitro-2-methylpropanol. Strips of tissue paper were dipped in the above solution, withdrawn, and the excess solution gently scraped off with a spatula. The

strips were immediately sprayed with acetone to hasten evaporation of the water. When dry, the strips were dipped in a saturated solution of paraffin wax in carbon tetrachloride and the latter allowed to evaporate at room temperature. Adhesive strips prepared in this manner were treated as in Example 1. It wasnoted that not only were good bonds obtained, but that the bond held firmly even while hot, thus eliminating the necessity of a short cooling period.

Example 5.-A syrupy liquid was prepared which contained the following ingredients:

The acetal of 2-nitro-i2-ethylpropanediol- After the above materials were incorporated by thoroughly mixing, strips of tissue paper were immersed therein, withdrawn, excess liquid removed by gently scraping with a spatula, and finally the strips were sprayed with acetone to effect quick evaporation of water. Afterwards the dried resin-impregnated strips were dipped in a saturated solution of wax in carbon i tetrachloride. Evaporation of the latter at room temperature yielded wax-coated strips.

These strips furnished tight, secure bonds when subjected to'a heating and pressing opera- Strips of paper were impregnated with the syrupy composition, dried, thencoated with paramn wax, as described in'Example 1. l

Tests with these papers were made in the manner indicated in Example 1. It was found in this instance also that a secure and firm bond was obtained after the heating and pressing operation and then allowing the test pieces to cool for about 30 seconds.

tion as described in Example 1.

Example 6.-Adhesive strips were prepared from highly absorbent paper by immersing the latter in a liquid composition consisting of '15 parts of dried ureaeformaldehyde resin, 75 parts of water, and 4.5 parts of Z-nitro-Z-methylpropanediol-1,3; then passing the paper strips through squeeze rolls to remove excess liquid;

, spraying the strips with acetone; allowing them Example 3.-The syrupy soluticn in this into dry i 5 finally coating them with a. thin film of wax by immersion in a carbon tetrachloride solution of paraiiin, withdrawing and permittingthe tetrachloride to evaporate spontaneously.

The nitroglycol, 2-nitro-2r-methylpropanediol- 1.3.,was made by condensation of 1 mole of nitroethane with 2 moles .of formaldehyd using a small quantity of as the catalyst.

composition was temperature.

Example 7.Another liquid composition applicable for the preparation of adhesive strips contained the following ingredients.

. Parts Dried urea-formaldehyde resin '15 Water 75 2-nitro-2-methylpropanediol-l,3 3 (him arabii- V 2 Strips of absorbent paper were immerseddn this liquid composition and then run through'squeeze' rolls. Afterwardsthey were sprayed, dried and coated with a film of wax as pie 6.

Example 8.An adhesive composition containing the following ingredients was prepared:

Parts Dried urea-formaldehyde resin 7 Water I 50 2-nitrobutyl acetate 4.5

One side of a sheet of absorbent paper was painted with suflicient' quantity of the above adhesive composition to secure a thin film. The

paraflin then was treated with acetic anhydride to yield the corresponding acetate.

The dried adhesive strip was placed on a small described in Exam position consisting of a thermosetting synthetic resin which is in the fusible state and a hardening agent therefor. The latter includes various I ultra-alcohols, nitroglycols or other polyhydroxy nitroparatlins, aliphatic carboxylic esters thereof, and l,l-di(nitroalkoxy) alkanes made by the phatic aldehyde.

interaction of a nitrohydroxy parafiln (nitroalcohol or polyhydroxy nitroparaflin) with an all- Such adhesive compositions when spread as a thin film on a suitable backing such as paper, wood, etc., and coated with a thin film of wax furnishes a bonding and/or adhes'ive agent suitable for many purposes. Fur- In effecting adhesion between the binding agent and other suitable material, it is n block of wood with the resin-coated side next to the wood. A heated iron was rubbed by hand over the paper for a few seconds, some pressure being exerted simultaneously with the heating operation. An excellent bond between the paper and wood was secured. v

Example 9.-Another portion of the paper, as prepared in Example 8, was placed on a piece 4 of cotton fabric, the resin-coated side being in contact with the fabric.

After subjecting the paper to a mild heating and pressure operation,

-.it was noted that a good bond was secured between the paper and fabric. This bond, however, was not permanent, as in the case of paper to paper. However, it would serve in cases where labels were to be attached to fabrics and then later removed, as both of these steps could be eil'ectedwithout damage to the fabric.

Example 10.-0ne side of a block of white pine was painted with the syrupy composition as prepared in Example 8. The resinous him on the wood then was sprayed with acetone and per.- mitted to dry (by evaporation of the liquids) at room temperature. When dry, the resin-coated side of the wood block was immersed in a saturated solution of paraffin wax in carbon tetrachloride, withdrawn,

When an untreated (i. e., 'not resin-coated) and allowed to dry at room Y troparaflin and an acyclic aldehyde, said compothin film and subjected tothe action of mild' heating and pressure.

piece of paper was placed on this block in contact with the adhesivevfilm and a hot hand iron was applied for a few seconds to the outer surface of the untreated paper, an excellent bond was effected between the paper and wood.- This bond could not be broken by pulling the paper from the wood; instead the paper split and tore. From the foregoing disclosure it will be seen that this invention comprises anadhesive comthermore, such.agents retain their adhesive or binding properties for an indeterminate time, as

for example, several weeks or months, or more.

to subject these two components in contact with one another to a mild heating and pressure operation.

What I claim is:

1. A heat-hardening adhesive composition which comprises a thermo-setting resin derived from urea and an acyclic aldehyde and a hardening agent therefor selected from the group consisting of nitrohydroxy parailins derived from a. nitroparailin and an acyclic aldehyde,

said composition being substantially a dry solid and covered with a coating of wax and being capable of conversion to an infusible state when spread in a thin film and subjected to the action of mild heating and pressure;

2. A heat-hardening ,adhesive composition which comprises a thermo-setting resin derived from urea and formaldehyde and a hardening agent therefor selected from the group consisting of nitrohydroxy paraflins derived from anisition being substantially a dry solid and covered with a coating of wax and being capable of conversion to an infusible state when spread in a 3. A heat-hardening adhesive composition which comprises a thermo-setting resin derived from urea and formaldehyde and a hardening agent therefor selected from the group consisting of nitroalcohols derived from anitroparaflin and an acyclic aldehyde, said composition being substantially a dry solid and covered with a coating of wax and being capable of conversion to an infusible state when spread in a thin film and subjected tothe action of mild heating and pressure.

4. A heat-hardening adhesive composition.

which comprises a thermo-setting resin derived from urea and formaldehyde and a hardening agenttherefor selected from the group consisting of nitroglycols derived from a nitroparafiln and an acyclic aldehyde, said composition being substantially a dry solid and covered with a coating of wax and being capable of conversion I to an infusible state when spread in a thin film and subjected to the action of mild heating and pressure. 5. A heat-hardening adhesive composition.

according to claim 3, in which the hardening agent is a nitrohydroxy paraflin derived from a nitroparaflin and formaldehyde.

6. A heat-hardening adhesive. composition,

- according to claim 3, in which the hardening agent is a nitrohydroxy paraflln derived from a nitroparsffiin and acetaldehyde. v

- CARI-EI'ON ELLIS. 

